CN114671832B - Method for continuously preparing furfural by utilizing microchannel reaction device - Google Patents
Method for continuously preparing furfural by utilizing microchannel reaction device Download PDFInfo
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- CN114671832B CN114671832B CN202210219925.XA CN202210219925A CN114671832B CN 114671832 B CN114671832 B CN 114671832B CN 202210219925 A CN202210219925 A CN 202210219925A CN 114671832 B CN114671832 B CN 114671832B
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- furfural
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- xylose
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- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 99
- 238000000034 method Methods 0.000 title claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 22
- 239000000376 reactant Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 20
- 150000002972 pentoses Chemical class 0.000 claims abstract description 15
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 239000012074 organic phase Substances 0.000 claims description 31
- 230000008569 process Effects 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 14
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical group CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000005215 recombination Methods 0.000 claims description 4
- 230000006798 recombination Effects 0.000 claims description 4
- 239000011831 acidic ionic liquid Substances 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 150000002191 fatty alcohols Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 14
- 239000000839 emulsion Substances 0.000 abstract description 4
- 238000004945 emulsification Methods 0.000 abstract 1
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 78
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 39
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 39
- 239000000243 solution Substances 0.000 description 24
- 239000012071 phase Substances 0.000 description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000008346 aqueous phase Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000004939 coking Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 5
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 5
- 230000001804 emulsifying effect Effects 0.000 description 5
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- HDKKRASBPHFULQ-UHFFFAOYSA-N 3-Hydroxy-2-pentanone Chemical compound CCC(O)C(C)=O HDKKRASBPHFULQ-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 2
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000013064 chemical raw material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- -1 pharmacy Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- MGADZUXDNSDTHW-UHFFFAOYSA-N 2H-pyran Chemical compound C1OC=CC=C1 MGADZUXDNSDTHW-UHFFFAOYSA-N 0.000 description 1
- DSMRYCOTKWYTRF-UHFFFAOYSA-N 3-methylfuran-2-carbaldehyde Chemical compound CC=1C=COC=1C=O DSMRYCOTKWYTRF-UHFFFAOYSA-N 0.000 description 1
- 229940124321 AIDS medicine Drugs 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 229920002527 Glycogen Polymers 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000002816 fuel additive Substances 0.000 description 1
- 239000007849 furan resin Substances 0.000 description 1
- 229940096919 glycogen Drugs 0.000 description 1
- 229910000856 hastalloy Inorganic materials 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
- C07D307/48—Furfural
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Furan Compounds (AREA)
Abstract
The invention discloses a method for continuously preparing furfural by utilizing a microchannel reaction device, which comprises the step of reacting a first reactant containing pentose and water with a second reactant containing an organic solvent and/or an emulsifying agent in the microchannel reaction device to obtain a reaction liquid containing furfural. According to the method provided by the invention, the emulsifier is added into the multiphase solvent reaction system to form the emulsion of oil-in-water (O/W) and water-in-oil (W/O), the reaction and separation of the furfural are realized at a molecular level, the micro-mixer structure of the micro-channel is a good emulsification reactor, the smooth operation of the whole system is realized, and meanwhile, the conversion rate of pentose and the yield of the furfural are improved.
Description
Technical Field
The invention belongs to the field of chemical synthesis and technology, and in particular relates to a method for continuously preparing furfural by utilizing a microchannel reaction device.
Background
Furfural also known as furaldehyde (C) 5 H 4 O 2 ) The relative molecular weight is 96.08, is an important organic chemical raw material, and is widely applied to petroleum, steel, pharmacy, fine chemicals and other aspects. Furfural is mainly prepared by dehydrating and cyclizing pentose liquid obtained by hemicellulose hydrolysis. China is a large country for producing furfural, and the mass production reaches 50 ten thousand tons per year, wherein 20% of the China is used for export. Furfural is used as an important organic chemical raw material and is mainly used for preparing furfuryl alcohol, wherein furfuryl alcohol is the main raw material for preparing furan resin, and furfuroic acid, furan and methyl furfurol are also prepared in addition to furfurolThe main raw materials of the pyran, the methyltetrahydrofuran and the acetyl propanol can be used for preparing products such as spice, bactericide, preservative, anti-AIDS drug, fuel additive, nylon, rubber and the like, and can be effectively utilized in various fields.
The production mode of furfural is divided into two types according to the reaction process, namely a one-step method and a two-step method. Representative processes for one-step processes include the Quaker Oats process, the Agrifuran process, the Petrole-Chemie process, the Escher Wyss process and the Rosenlew process, wherein the one-step process has a large number of industrial applications due to low equipment investment and simple operation. However, in the traditional one-step method, biomass is directly used as a raw material in the process of producing furfural, a large amount of steam is consumed in the reaction, and a large amount of waste water and solid slag are generated at the same time, wherein the waste water is mainly acid-containing waste water, and the solid slag is mainly unhydrolyzed cellulose, lignin, organic acid generated in the process and the like. Therefore, the separation of lignocellulose components is realized by combining with the biorefinery process, and the development of the process for producing furfural by a two-step method can reduce the environmental pollution degree and increase the resource utilization degree. However, the two-step method has high control over the reaction process and equipment investment, and the problems of low reaction continuity, serious furfural side reaction, overhigh cost of a reaction system and the like mainly exist at present, so that the industrial production is not effectively utilized.
The problems of complex side reaction, serious carbonization and the like in the reaction process of preparing the furfural are main reasons for low furfural yield. In recent years, research has found that the side reaction of furfural is mainly condensation reaction of furfural and xylose intermediate, wherein the mode of inhibiting the side reaction is mainly a two-phase solvent method, and the generated furfural and xylose intermediate are timely separated through the extraction action of an organic solvent to inhibit the formation of carbonized products. However, in the pipeline of the tubular reactor, the two-phase solvent system mainly exists in a sectional form, the phenomenon seriously weakens the extraction effect of the two-phase system, the pipeline is blocked by the generation of the water-phase carbonization byproducts, the continuous reaction system is failed, the glycogen conversion rate in the process of preparing furfural in the prior art is low, and the furfural yield is not high. Therefore, the invention provides a method for continuously preparing furfural by utilizing a microchannel reactor so as to effectively solve the problems.
Disclosure of Invention
The invention aims to: the invention aims to solve the technical problem of providing a method for continuously preparing furfural by utilizing a microchannel reaction device aiming at the defects of the prior art.
The invention is characterized in that: in a single-water-phase microchannel reactor, coking matters are generated when pentose is converted to prepare furfural, so that the tubular reactor is blocked, and the reaction fails. The research adopts a multiphase solvent system to realize that the organic solvent is used for extracting furfural and separating the furfural from the water phase in the reaction process, so that the coking phenomenon is reduced. However, the multiphase solvent system is mixed by the mixer, and then the phenomena of sectional flow (organic phase-water phase-organic phase-water phase) and the like can occur in the pipeline, so that the extraction efficiency of the organic solvent is poor, the reaction effect is poor, and the continuous reaction is influenced. As shown in figure 1, the multiphase solvent emulsifying system developed in the research is characterized in that an emulsifying agent is added into a multiphase solvent reaction system to form an emulsion of oil-in-water (O/W) and water-in-oil (W/O), the reaction and separation of furfural are realized at a molecular level, and a micro-mixer structure of a micro-channel is a good emulsifying reactor, so that the smooth operation of the whole system is realized, and meanwhile, the conversion rate of pentose and the yield of furfural are improved.
In order to solve the technical problems, the invention discloses a method for continuously preparing furfural by utilizing a microchannel reaction device.
In some embodiments, the preparation method comprises reacting a first reactant containing pentose and water with a second reactant containing an organic solvent and/or an emulsifier in a microchannel reactor to obtain a reaction solution containing furfural; in some embodiments, the preparation method comprises reacting a first reactant containing pentose, water and acid with a second reactant containing an organic solvent and an emulsifier in a microchannel reactor to obtain a reaction solution containing furfural.
In some embodiments, the pentose and water in the first reactant are either prepared from a configuration, or are xylose liquor, biomass, and hydrolysate.
In some embodiments, the concentration of pentose in the first reactant is 20 to 100g/L; in some embodiments, the concentration of pentose in the first reactant is 30 to 50g/L; in some embodiments, the concentration of pentose in the first reactant is 40g/L.
In some embodiments, the catalyst is any one or a combination of several of sulfuric acid, phosphoric acid, heteropolyacid and acidic ionic liquid; wherein the heteropoly acid includes, but is not limited to, phosphotungstic acid, silicotungstic acid; wherein the acidic ionic liquid includes but is not limited to + [Bmim][HSO 3 ] - 、 + [Bmim][PF 6 ] - 、 + [Bmim][BF 4 ] - Etc.; in some embodiments, the catalyst is + [Bmim][PF 6 ] - 。
In some embodiments, the molar concentration of acid protons in the catalyst is 0.1-2mol/L of the first reactant; in some embodiments, the molar concentration of acid protons in the catalyst is 0.2mol/L.
In some embodiments, the organic solvent is any one or a combination of butanol, dimethyl carbonate, diethyl carbonate, xylene, ethyl acetate, n-hexane, toluene, methyl isobutyl ketone, methyl tetrahydrofuran, and diethylene glycol butyl ether acetate; in some embodiments, the organic solvent is 2-methyltetrahydrofuran and/or diethylene glycol butyl ether acetate; in some embodiments, the organic solvent is diethylene glycol butyl ether acetate.
In some embodiments, the emulsifier is any one or a combination of several of alkylphenol ethoxylates (OP, TX series), fatty alcohol ethoxylates (MOA series), tween (T series) and span (S series); in some embodiments, the emulsifier is any one or a combination of several of OP-10, OP-40 and OP-50.
In some embodiments, when the second reactant contains both an organic solvent and an emulsifier, the organic solvent volume to emulsifier volume to mass ratio is 100ml:1-20g; in some embodiments, when the second reactant contains both an organic solvent and an emulsifier, the organic solvent volume to emulsifier volume to mass ratio is 100ml:5g.
In some embodiments, the microchannel reaction device comprises a micromixer that is any of a split recombination micromixer (CPMM-R300), an inter-digitated micromixer (SIM-V2), and an impinging stream micromixer (IJMM); in some embodiments, the micromixer is a split recombination micromixer (CPMM-R300).
In some embodiments, the ratio of the volume flow rates of the first reactant and the second reactant into the microchannel reactor is controlled to be 1 (0.8-2); in some embodiments, the volumetric flow ratio of the first reactant and the second reactant into the microchannel reactor is controlled to be 1:1.
In some embodiments, the temperature of the reaction is 160 to 200 ℃; in some embodiments, the temperature of the reaction is 180 ℃.
In some embodiments, the residence time of the reaction is from 5 to 20 minutes; in some embodiments, the residence time of the reaction is 15 minutes.
In some embodiments, after the reaction is finished, cooling, demulsification or non-demulsification and liquid separation are performed on the reaction liquid containing furfural, and organic phase distillation is performed to obtain furfural.
In some embodiments, the demulsification process is with or without demulsifiers.
In some embodiments, when the system is oil-in-water, the demulsifier is an inorganic acid, ferric sulfate, aluminum sulfate, or the like; in some embodiments, where the system is oil-in-water, the demulsifier is aluminum sulfate.
In some embodiments, where the system is water-in-oil, the demulsifier is an anionic and nonionic surfactant such as ammonium lauryl sulfate; in some embodiments, where the system is water-in-oil, the demulsifier is ammonium lauryl sulfate.
The beneficial effects are that: compared with the prior art, the invention has the main advantages that:
1, developing a continuous micro-channel reaction system, solving the problem of intermittent production by a traditional one-step method or a two-step method, and realizing the idea of continuously preparing furfural from pentose liquid in a tubular reactor;
2, a multiphase solvent system is developed, continuous reaction separation coupling of a tubular reaction system is realized, a large amount of coking phenomenon is avoided, and the yield of furfural is increased;
3, a multiphase solvent system of diethylene glycol butyl ether acetate is developed, the problem of the danger of experimental equipment with high saturated vapor pressure of a conventional organic solvent at high temperature is avoided, and meanwhile, the reaction efficiency is improved;
4, developing a micro-channel multiphase solvent emulsifying system, wherein the micro-channel is a good emulsifying reactor, and the emulsifying system realizes the reaction separation coupling effect of converting pentose into furfural from a molecular layer, avoids coking and greatly improves the yield.
Drawings
The foregoing and/or other advantages of the invention will become more apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a schematic diagram of a microchannel reactor and a conversion scheme during the reaction.
FIG. 2 is a schematic diagram showing the result of liquid phase detection of the reaction liquid.
Detailed Description
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The microchannel reaction device described in the following examples comprises: the micro-mixer is connected with the micro-channel reactor, the back pressure valve and the collector in series in sequence. Wherein the micromixer types include a split recombination micromixer (CPMM-R300), an internal interdigital micromixer (SIM-V2), or an impinging stream micromixer (IJMM), available from Ehrfeld Mikrotechnik BTS GmbH; the temperature control system is used for controlling the temperature in an oil bath pot; the flow interval of the advection pump is 0.01-50mL/min, and the advection pump is purchased from Sanotac (third technology); the back pressure valve is made of hastelloy, and the interval is 0-6MPa; the micro-channel is made of PTFE, the pipe diameter is 2mm, the total reaction volume is 90mL, and the reaction retention time is controlled by controlling the flow rate.
The conversion rate of xylose and the yield of furfural were calculated as follows:
xylose conversion (%) = (molar xylose consumed per total molar xylose consumed by the reaction) ×100%
Furfural yield (%) = (molar amount of furfural produced by reaction)/(molar amount of total xylose×0.64) ×100%.
Examples 1 to 24:
a40 g/L xylose aqueous solution and a 10g/L sulfuric acid solution (proton acid concentration: about 0.2 mol/L) were placed in a sugar solution tank, and a methyl isobutyl ketone (MIBK) solvent was added to an organic solvent tank. After CPMM-R300, SIM-V2 and IJMM are mixed, the mixture is pumped into micro-channel reaction equipment according to a flow rate ratio of 1:1, the temperature is 160 ℃, 170 ℃, 180 ℃, 190 ℃ and the reaction time is 10min and 15min respectively. After the reaction is finished, cooling and separating a reaction liquid containing furfural to obtain a water phase and an organic phase, detecting the content of xylose and furfural in the water phase, detecting the content of furfural in the organic phase, distilling the organic phase, and collecting the furfural in the organic phase. The conversion of xylose to the reaction solution and the total yield of organic and aqueous phases obtained under different conditions are shown in table 1 below; the results of liquid phase detection of the organic phase reaction solution obtained in example 6 are shown in FIG. 2.
TABLE 1 conversion of xylose and Furfural yield in examples 1-24
Examples 25 to 30:
a xylose aqueous solution (40 g/L) and a sulfuric acid aqueous solution (10 g/L) (proton acid concentration: about 0.2 mol/L) were placed in a sugar solution tank, and dimethyl carbonate, diethyl carbonate, toluene, xylene, 2-methyltetrahydrofuran, diethylene glycol butyl ether acetate were placed in an organic solvent tank, respectively. After mixing by CPMM-R300, pumping into a microchannel reactor according to a flow rate ratio of 1:1, wherein the temperature is 180 ℃, and the reaction time is 15min respectively. After the reaction is finished, cooling and separating a reaction liquid containing furfural to obtain a water phase and an organic phase, detecting the content of xylose and furfural in the water phase, detecting the content of furfural in the organic phase, distilling the organic phase, and collecting the furfural in the organic phase. The conversion of xylose to the reaction solution and the total yield of organic and aqueous phases obtained under different conditions are shown in table 2 below.
TABLE 2 conversion of xylose and Furfural yield in examples 25-30
| Examples | Organic solvents | Xylose conversion | Furfural Total yield (aqueous phase+organic phase) |
| 25 | Dimethyl carbonate | 96.8％ | 74.85％ |
| 26 | Diethyl carbonate | 97.2％ | 76.29％ |
| 27 | Toluene (toluene) | 98.9％ | 80.42％ |
| 28 | Xylene (P) | 98.6％ | 80.21％ |
| 29 | 2-methyltetrahydrofuran | 99.2％ | 83.02％ |
| 30 | Diethylene glycol butyl ether acetate | 99.3％ | 85.89％ |
Examples 31 to 35:
in a sugar solution storage tank, 40g/L xylose solution and catalyst solutions with different concentrations (molar concentration of acid protons is about 0.2 mol/L) are arranged, and the catalyst systems are respectively as follows: no catalyst, sulfuric acid, phosphoric acid, silicotungstic acid, phosphotungstic acid, + [Bmim][PF 6 ] - Wherein the multiphase solvent tank is configured as diethylene glycol butyl ether acetate. After mixing by CPMM-R300, pumping into a microchannel reactor according to a flow rate ratio of 1:1, wherein the temperature is 180 ℃, and the reaction time is 15min respectively. After the reaction is finished, cooling and separating a reaction liquid containing furfural to obtain a water phase and an organic phase, detecting the content of xylose and furfural in the water phase, detecting the content of furfural in the organic phase, distilling the organic phase, and collecting the furfural in the organic phase. The conversion of xylose to the reaction solution and the total yield of organic and aqueous phases obtained under different conditions are shown in table 3 below.
TABLE 3 conversion of xylose and Furfural yield in examples 31-35
| Examples | Catalyst | Xylose conversion | Furfural Total yield (aqueous phase+organic phase) |
| 31 | Without any means for | 80.6％ | 76.65％ |
| 30 | Sulfuric acid | 99.3％ | 85.89％ |
| 32 | Phosphoric acid | 92.3％ | 78.46％ |
| 33 | Silicotungstic acid | 97.7％ | 90.37％ |
| 34 | Phosphotungstic acid | 98.6％ | 91.73％ |
| 35 | + [Bmim][PF 6 ] - | 99.1％ | 93.34％ |
Examples 36 to 43:
and preparing a xylose aqueous solution with the concentration of 40g/L and phosphotungstic acid with the concentration of acid protons of about 0.2mol/L in a sugar solution storage tank, wherein the multiphase solvent storage tank is prepared from diethylene glycol butyl ether acetate, and emulsifying agents MOA-9, OP-10, OP-40, OP-50, tween-85, tween-80, span-60 and span-85 are added, wherein the volume preparation amount ratio of the diethylene glycol butyl ether acetate to the emulsifying agents is 100 mL/5 g. After mixing by CPMM-R300, pumping into a microchannel reactor according to a flow rate ratio of 1:1, wherein the temperature is 180 ℃, and the reaction time is 15min respectively. After the reaction is finished, cooling a reaction liquid containing furfural, breaking or not breaking emulsion, separating the reaction liquid to obtain a water phase and an organic phase, detecting the content of xylose and furfural in the water phase, detecting the content of furfural in the organic phase, distilling the organic phase, and collecting the furfural in the organic phase; wherein, if the reaction effluent can automatically split phases, no emulsifying agent is added for demulsification, if the reaction effluent is still in an emulsified state, ammonium dodecyl sulfate is added for stirring or vibration demulsification. The conversion of xylose to the reaction solution and the total yield of organic and aqueous phases obtained under different conditions are shown in table 4 below.
TABLE 4 conversion of xylose and Furfural yield in examples 36-43
Example 44:
a40 g/L xylose aqueous solution is prepared in a sugar solution storage tank without a catalyst, wherein the multiphase solvent storage tank is prepared from diethylene glycol butyl ether acetate and an emulsifier OP-10 is additionally arranged. After mixing by CPMM-R300, pumping into a microchannel reactor according to a flow rate ratio of 1:1, wherein the temperature is 180 ℃, and the reaction time is 20min respectively. After the reaction is finished, cooling a reaction liquid containing furfural, breaking or not breaking emulsion, separating the reaction liquid to obtain a water phase and an organic phase, detecting the content of xylose and furfural in the water phase, detecting the content of furfural in the organic phase, distilling the organic phase, and collecting the furfural in the organic phase; wherein, if the reaction effluent can automatically split phases, no emulsifying agent is added for demulsification, if the reaction effluent is still in an emulsified state, ammonium dodecyl sulfate is added for stirring or vibration demulsification. The reaction solution was taken for HPLC detection, the xylose conversion was 93.6%, and the furfural yield was 87.72%.
Comparative example 1:
2.4g of xylose and 60mL of 1% (the concentration of protonic acid is about 0.2 mol/L) sulfuric acid aqueous solution are added into a reaction kettle, the reaction is carried out for 2 hours at 170 ℃, after the reaction is finished, the coking phenomenon is serious, the reaction liquid is taken for HPLC detection, the xylose conversion rate is 100%, and the furfural yield is 36.3%.
Comparative example 2:
2.4g of xylose, 30mL of 1% (the concentration of protonic acid is about 0.4 mol/L) sulfuric acid aqueous solution and 30mL of methyl isobutyl ketone are added into a reaction kettle, the reaction is carried out for 2 hours at 170 ℃, after the reaction is finished, the phase separation interface has a little coking phenomenon, the reaction liquid (aqueous phase and organic phase) is respectively subjected to HPLC detection, the xylose conversion rate is 100%, and the furfural yield is 78.1%.
Comparative example 3:
preparing 40g/L xylose solution and 10g/L sulfuric acid solution (with the concentration of protonic acid being about 0.2 mol/L) in a sugar solution storage tank, pumping the xylose solution and the sulfuric acid solution into a micro-channel reactor through a advection pump, wherein the reaction temperature of the micro-channel is 170 ℃, the reaction retention time is 10min, the reaction solution is partially coked in the flowing process, a pipeline is blocked, the reaction is continuous, partial reaction solution in a reactor section is taken for detection, the xylose conversion rate is 80%, and the furfural yield is 48.4%.
Comparative example 4:
xylose, phosphotungstic acid and water are added into a reaction kettle, so that the concentration of the xylose is 40g/L, the molar concentration of acid protons is about 0.2mol/L,30mL of diethylene glycol butyl ether acetate, OP-10 emulsifier is 1.67g, the reaction is carried out for 2 hours at 180 ℃, after the reaction is finished, the reaction is cooled to room temperature, ammonium dodecyl sulfate is added for stirring and demulsification, the reaction solutions (aqueous phase and organic phase) are respectively taken for HPLC detection, the xylose conversion rate is 100%, and the total furfural yield is 82.14%.
The invention provides a method for continuously preparing furfural by utilizing a microchannel reaction device, and a method for realizing the technical scheme, wherein the method and the way are a plurality of, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by one of ordinary skill in the art without departing from the principle of the invention, and the improvements and modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (8)
1. A method for continuously preparing furfural by utilizing a microchannel reactor is characterized in that a first reactant containing a catalyst, pentose and water reacts with a second reactant containing an organic solvent and an emulsifying agent in the microchannel reactor to obtain a reaction liquid containing furfural;
the catalyst is heteropolyacid and/or acidic ionic liquid;
the molar concentration of acid protons in the catalyst is 0.1-0.2mol/L;
the emulsifier is alkylphenol ethoxylates and/or fatty alcohol ethoxylates;
the organic solvent is diethylene glycol butyl ether acetate;
the volume-mass ratio of the organic solvent to the emulsifier is 100mL (1-20 g);
the microchannel reaction device comprises a micromixer, wherein the micromixer is a separation recombination type micromixer.
2. The method of claim 1, wherein the concentration of pentose in the first reactant is 20 to 100g/L.
3. The method according to claim 1, wherein the emulsifier is of MOA series and/or OP series.
4. The method of claim 1, wherein the emulsifier is any one or a combination of several of MOA-9, OP-10, OP-40 and OP-50.
5. The method of claim 1, wherein the ratio of the volume flow rates of the first reactant and the second reactant into the microchannel reactor is controlled to be 1 (0.8-2).
6. The method according to claim 1, wherein the temperature of the reaction is 160-200 ℃.
7. The process according to claim 1, wherein the residence time of the reaction is from 5 to 20min.
8. The method of claim 1, wherein after the reaction is finished, the reaction liquid containing furfural is cooled, demulsified or not demulsified and separated, and the organic phase is distilled to obtain furfural.
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